Recovery of inorganic salt during processing of lignocellulosic feedstocks

ABSTRACT

A method for recovering inorganic salt during processing of a lignocellulosic feedstock is provided. The method comprises pretreating the lignocellulosic feedstock by adding an acid to the feedstock to produce a pretreated lignocellulosic feedstock. A soluble base is then added to the pretreated lignocellulosic feedstock to adjust the pH and produce a neutralized feedstock. The neutralized feedstock is then enzymatically hydrolyzed to produce an enzyme hydrolyzed feedstock and a sugar stream. Inorganic salt is recovered from either a stream obtained from the lignocellulosic feedstock prior to the step of pretreating, a stream obtained from the pretreated lignocellulosic feedstock, a stream obtained from the neutralized feedstock, a stream obtained from the sugar stream, or a combination of these streams. The inorganic salt may be concentrated, clarified, recovered and purified by crystallization, electrodialysis drying, or agglomeration and granulation, and then used as desired, for example as a fertilizer.

RELATED APPLICATION

This application is a division of application Ser. No. 12/539,645 filedAug. 12, 2009, which in turn is a division of application Ser. No.11/104,698, filed Apr. 13, 2005 (now U.S. Pat. No. 7,585,652), which inturn claims the priority benefit of a provisional application No.60/561,787, filed Apr. 13, 2004, all of which are incorporated byreference herein.

FIELD OF INVENTION

The present invention relates to a method for processing lignocellulosicfeedstocks. More specifically, the present invention provides a methodfor recovering inorganic salt during the processing of lignocellulosicfeedstocks.

BACKGROUND OF THE INVENTION

Fuel ethanol is currently made from feedstocks such as corn starch,sugar cane, and sugar beets. The production of ethanol from thesesources cannot grow much further, as most of the farmland suitable forthe production of these crops is in use. In addition, these feedstockscan be costly since they compete with the human and animal food chain.Finally, the use of fossil fuels, with the associated release of carbondioxide and other products, for the conversion process is a negativeenvironmental impact of the use of these feedstocks.

The production of fuel ethanol from cellulosic feedstocks provides anattractive alternative to the fuel ethanol feedstocks used to date.Cellulose is the most abundant natural polymer, so there is an enormousuntapped potential for its use as a source of ethanol. Cellulosicfeedstocks are also inexpensive, as they do not have many other uses.Another advantage of producing ethanol from cellulosic feedstocks isthat lignin, which is a byproduct of the cellulose conversion process,can be used as a fuel to power the conversion process, thereby avoidingthe use of fossil fuels. Several studies have concluded that, when theentire cycle is taken into account, the use of ethanol produced fromcellulose generates close to nil greenhouse gases.

The cellulosic feedstocks that are the most promising for ethanolproduction include (1) agricultural wastes such as corn stover, wheatstraw, barley straw, canola straw, rice straw, and soybean stover; (2)grasses such as switch grass, miscanthus, cord grass, and reed canarygrass, (3) forestry wastes such as aspen wood and sawdust, and (4) sugarprocessing residues such as bagasse and beet pulp.

Regardless of the feedstock used, the first step involves handling andsize reduction of the material. The feedstock must be conveyed into theplant. This is contemplated to be carried out by trucks, followed byplacing the feedstock on conveyor belts to be conveyed into the plant.The feedstock particles must then be reduced to the desired size to besuitable for handling in the subsequent processing steps.

The first process step is a chemical treatment, which usually involvesthe use of steam along with acid or alkali to break down the fibrousmaterial. The chemical treatment is carried out for either of twoprimary processes—acid hydrolysis and enzymatic hydrolysis—used toconvert the feedstock to sugar.

In the acid hydrolysis process, the feedstock is subjected to steam andsulfuric acid at a temperature, acid concentration, and length of timethat are sufficient to hydrolyze the cellulose to glucose andhemicellulose to xylose and arabinose. The sulfuric acid can beconcentrated (25-90% w/w) or dilute (3-8% w/w). The glucose, xylose andarabinose are then fermented to ethanol using yeast, and the ethanol isrecovered and purified by distillation. A problem with concentrated acidhydrolysis is that the high levels of concentrated acid requirednecessitate the recovery and re-use of over 99% of the acid in theprocess. The recovery of this high proportion of acid is especiallydifficult due to the high viscosity and corrosivity of concentratedacid.

In the enzymatic hydrolysis process, the steam temperature,concentration of acid, and treatment time are chosen to be significantlymilder than that in the acid hydrolysis process, such that the exposedcellulose surface area is greatly increased as the fibrous feedstock isconverted to a muddy texture. Much of the hemicellulose is hydrolyzed,but there is little conversion of the cellulose to glucose. Thecellulose is hydrolyzed to glucose in a subsequent step that usescellulase enzymes, and the steam/acid treatment in this case is known aspretreatment. The acids used in pretreatment include sulfuric acid insteam explosion and batch and continuous flow pretreatments and alsosulfurous acid and phosphoric acid.

The hydrolysis of the cellulose, whether by acid hydrolysis or bycellulase enzymes after pretreatment, is followed by the fermentation ofthe sugar to ethanol. The ethanol is then recovered by distillation.

There are several problems that must be overcome in order for theconversion of cellulosic biomass to sugar or ethanol to be commerciallyviable. In particular, there is a large amount of inorganic salt presentin the feedstock and generated in the process. The inorganic salt has anadverse impact on the pretreatment, enzymatic hydrolysis, and yeastfermentation processes. In addition, the purchase of the acid and thealkali and the disposal of the salt is costly.

Neutral salts consist of cation(s), which provide a positive charge, andanion(s), which provide a negative charge. The most prevalent element inthe feedstock that is a source of cations is potassium. Other elementsin the feedstocks that are significant sources of cations includecalcium, sodium, and magnesium, at concentrations of about ⅓, 1/7, and1/10 that of potassium. Most of the potassium, calcium, sodium, andmagnesium in the feedstocks is complexed with organic compounds, such asproteins or carboxylic acids, or exists in the form of oxides oroxlates. The feedstocks are slightly alkaline with this “excess” ofcations, as the concentration of anions is low.

The addition of, for example, sulfuric acid to the feedstock as part ofthe chemical treatment forms the mixtures of sulfuric acid and acidifiedsulfate salts, which include potassium bisulfate, calcium sulfate,sodium bisulfate, and magnesium bisulfate. Analogous acidified salts areformed with the use of other acids. These acidified salts are more watersoluble than the complexed cations, and are released into solution uponacid addition. The presence of the cations thereby increases the amountof acid required in the chemical treatment. The high acid and acidicsalt concentrations result in some degradation of sugar, includingxylose, during the pretreatment.

The acid used in the pretreatment must be neutralized prior to theenzymatic hydrolysis of the cellulose or fermentation of the sugar.Cellulase enzymes produced by the fungus Trichoderma, which are theleading sources of cellulase for cellulose conversion, exhibit optimumactivity at pH 4.5 to 5.0. These enzymes exhibit little activity belowpH 3. Microbes that ferment the sugar include yeast and Zymomonasbacteria. The yeast are active at pH 4-5 while the Zymomonas are activeat pH 5-6. An acidic chemical treatment is often carried out at a pH ofabout 0.8 to 2.0, so a significant amount of alkali must be added toincrease the pH to the range that is required for microbial fermentationand enzymatic hydrolysis.

When an acidic pretreatment is carried out, the alkaline that is usuallyused for neutralization of the acid is sodium hydroxide, but potassiumhydroxide and ammonium hydroxide have also been reported. The highlevels of these compounds that are required increase the cost of theprocess.

Although the neutralized slurry is at a pH range that is compatible withyeast or fermenting bacteria or cellulase enzymes, the inorganic saltconcentration is high enough to be inhibitory to the microbes orenzymes. The inorganic salt can also cause a degradation of the sugar,particularly the xylose, in evaporation and distillation processes thatare carried out downstream of the hydrolysis.

Alkali that is used during processing of the lignocellulosic feedstockcan be either soluble or insoluble. An example of an insoluble alkali islime, which is used to precipitate inhibitors of cellulase enzymesarising from the pretreatment. This process is known as over-liming andinvolves adding lime to the pretreated feedstock until an alkaline pH ofbetween 9 and 12 is achieved. The limed material is then adjusted to pH5 prior to enzyme hydrolysis using phosphoric acid, carbon dioxide orother convenient acids. Since overliming precipitates some of theinhibitors of the cellulase enzymes, it results in an improved enzymatichydrolysis of the cellulose with existing pretreatment technologies.However, there are numerous problems associated with overlimingincluding (1) disposal of the lime; (2) calcium precipitation whichleads to downstream scaling; (3) the expense of the lime; and (4) thefact that the treatment is not completely effective in removinginhibitors of enzymes and yeast.

Wooley et al. (In Lignocellulosic Biomass to Ethanol Process Design andEconomics Utilizing Co-Current Dilute Acid Prehydrolysis and EnzymeHydrolysis Current and Future Scenarios, (1999) Technical Report,National Renewable Energy Laboratory pp. 16-17) describe a process oftreating lignocellulosic material utilizing over-liming following acidpretreatment. Milled wood chips are first pretreated with dilutesulfuric acid followed by enzyme hydrolysis and fermentation. Followingpretreatment, the resulting liquid and solids are flash cooled tovapourize a large amount of water and inhibitors of the downstreamfermentation reaction. After ion exchange to remove acetic acid, thematerial is over-limed by adding lime to raise the pH to 10. The liquidis then adjusted to pH 4.5 which results in the formation of gypsumcrystals (CaSO₄). These crystals can be removed from the liquid byhydrocyclone and rotary drum filtration in series. Although the processdescribes the removal of gypsum after acid treatment, the investigatorsdo not address the problems associated with removal of insoluble calciumsalt.

U.S. Pat. No. 6,043,392 (Holtzapple et al.) employs a pretreatment stepwith lime prior to recovering volatile fatty acids produced during thefermentation of lignocellulosic biomass by anaerobic or thermophilicbacteria. After the treatment, lime is removed by draining thelime-containing water from the biomass, followed by fermentation withanaerobic bacteria. The anaerobic organisms then convert the biomass toorganic acids such as acetic acid, proprionic and butyric acids. Theorganic acids produced by these fermentation processes can beconcentrated and converted to ketones by pyrolysis in a thermalconverter. Any soluble and insoluble minerals present after pyrolysiscan be recovered and sold as a fertilizer. Alternatively, the organicacids are treated with a tertiary amine and carbon dioxide to produce anacid/amine complex that decomposes to form an acid and an amine withdifferent volatilities. The acid can then be separated from the amine bydistillation and precipitated minerals that accumulate in the bottoms ofthe distillation column can be recovered. Although Holtzapple et al.describe an effective method for the isolation of organic acids producedduring fermentation using an alkaline pretreatment, they do notdemonstrate the applicability of their process using an acidicpretreatment, nor did they demonstrate the effectiveness of theirpretreatment in improving enzymatic hydrolysis.

U.S. Pat. No. 6,478,965 (Holtzapple et al.) discloses a method forisolating carboxylate salts formed as a product during the fermentationof lignocellulosic biomass by anaerobic bacteria. A fermentation broth,which contains dilute carboxylate salt in aqueous solution, is contactedwith a low molecular weight secondary or tertiary amine which has a highaffinity for water and a low affinity for the carboxylate salt. Thisallows the water to be selectively extracted while the carboxylate saltremains in the fermentation broth and becomes concentrated so that itcan be easily recovered. The carboxylate salt may be furtherconcentrated by evaporation, dried or converted to a more concentratedcarboxylic acid solution. While Holtzapple et al. describe an effectivemethod for the isolation of carboxylate fermentation products, they donot address the recovery of inorganic salts from the feedstock itself orinorganic salts arising from the acids and bases used during theprocessing of the lignocellulosic feedstocks. Furthermore, the processdisclosed does not include a step of acidic pretreatment prior toenzymatic hydrolysis and fermentation.

U.S. Pat. No. 5,124,004 (Grethlein et al.) discloses a method forconcentrating an ethanol solution by distillation. The method firstinvolves partially concentrating the ethanol solution by distillationand withdrawing a vapour stream. Next, the condensation temperature ofthe vapour is raised above the evaporation temperature of a re-boilerliquid used in the process (a heat-sink liquid). The vapour stream isthen used to heat the re-boiler liquid and partially enriched vapour isthen removed and condensed. The condensed stream is introduced to anextractive distillation column and concentrated in the presence of anadded salt to increase the volatility of the ethanol. The inventionprovides the benefit that the heat requirement of distillation isreduced since vapour required to heat the system does not need to beprovided by an external source. However, there is no discussion ofrecovering and removing the salts added during the final distillationstep.

U.S. Pat. No. 5,177,008 (Kampen) discloses the recovery of fermentationby-products, namely glycerol, betaine, L-pyroglutamic acid, succinicacid, lactic acid and potassium sulfate, produced during the manufactureof ethanol from sugar beets. The process involves fermenting the rawmaterial, collecting the ethanol by distillation and then recovering theby-products in the remaining still bottoms. The by-products are isolatedby first centrifuging the still bottoms and performing microfiltrationto further clarify the solution. The resulting permeate is thenconcentrated to a solids concentration of 50-75%. The concentratedsolution is first subjected to a crystallization step to recoverpotassium sulfate and then passed to a chromatographic separation stepfor the subsequent recovery of glycerol, betaine, succinic acid,L-pyroglutamic acid or lactic acid. The potassium sulfate is present inthe raw material and its concentration is increased by cooling thesolution and/or by the addition of sulfuric acid as part of thecrystallization. The process of Kampen has several advantages such asenergy and water savings and high solids concentrations. However, thereis no discussion of a chemical pretreatment of lignocellulosic materialwith acid or an alkali neutralization step prior to enzymatic hydrolysisand fermentation and the associated problems with the presence of sodiumand magnesium salts arising from such a pretreatment. Furthermore, sinceKampen et al. used sugar beets, they were able to crystallize potassiumsulfate directly from the still bottoms, and they do not address therecovery from still bottoms of salt mixtures with high levels ofimpurities that do not crystallize. Acid pretreatment of lignocellulosicfeedstocks results in mixtures of inorganic salts in the still bottomsthat cannot be directly crystallized.

U.S. Pat. Nos. 5,620,877 and 5,782,982 (Farone et al.) disclose a methodfor producing sugars from rice straw using concentrated acid hydrolysiswhich, as set out above, is not a preferred pretreatment method. Themethod results in the production of quantitative yields of potassiumsilicate. In this method, the rice straw is treated with concentratedsulfuric acid at a concentration of between 25% and 90%. The resultingmixture is then heated to a temperature to effect acid hydrolysis of therice straw. Subsequently, the mixture is separated from the remainingsolids by pressing. The pressed solids can then be treated with 5% to10% sodium hydroxide to extract silicic acid. Following the treatmentwith sodium hydroxide, the solids are heated and then pressed and washedwith water to extract a liquid. The extracted liquid is then treatedwith an acid, which results in the formation of a precipitate that canbe separated by filtration. The filtered material is then treated withbleach to produce silica gel that can be further treated to producesodium silicate, potassium silicate or other useful materials. Themethod also employs a neutralization step using lime to precipitatesoluble inorganic salts present in a sugar stream produced duringfermentation. Lime is an insoluble base that can build up on processequipment downstream of its point of addition and decrease theefficiency of the process.

WO 02/070753 (Griffin et al.) discloses a leaching process to removealkali from lignocellulosic feedstocks thereby decreasing the acidrequirement for chemical treatment. The process includes milling thefeedstock, followed by preconditioning it with steam and then contactingthe feedstock with water to leach out the salts, protein, and otherimpurities. The water containing these soluble compounds is then removedfrom the feedstock. This process decreases the acid requirements in thesubsequent pretreatment process, which increases the yield of xyloseafter pretreatment. However, the costs and problems associated with thesalt arising from the acid or alkali added for chemical treatment andthe alkali or acid added after chemical treatment for adjustment of thepH are not addressed. Furthermore, disposing of the leachate isinconvenient and adds to the cost of the process.

U.S. Pat. No. 4,321,360 (Blount) discloses the preparation of ethanolfrom lignocellulosic feedstocks; however, there is no discussion of saltprocessing or recovery arising during this process. U.S. Pat. No.6,608,184 (Blount) describes the production of ethanol, salt, andseveral other organic products from sewer sludge comprising seweredcellulose waste material (rather than a lignin-cellulose material). Thisprocess involves mixing sewer sludge with water and sodium hydroxide, oran acid (sulfuric or hydrochloric acid). The slurry containing acid oralkali is then heated to hydrolyze the cellulose in the sludge, and anexcess of water is added to dissolve the organic compounds. The aqueousmaterial is then separated from the insolubles and evaporated toconcentrate the solution and crystallize out the carbohydrates. Thecarbohydrates are filtered off, slurried in water, and fermented toethanol using yeast. The aqueous solution containing ammonium sulfateand other compounds may then be used as a fertilizer. Alternatively, thesalt is separated from the sugar by membrane filtration and then thesalt is evaporated and dried.

U.S. Pat. No. 6,709,527 (Fechter et al.) discloses a process of treatingan impure cane-derived sugar juice to produce white sugar and whitestrap molasses. The process involves subjecting the sugar juice tomicrofiltration/ultrafiltration to decrease the levels of suspendedsolids, organic non-sugar impurities and/or colour. The sugar juice isnext subjected to ion exchange with a strong acid cation exchange resinin the hydrogen form and then to ion exchange with an anion ion exchangeresin in the hydroxide form. Potassium-based fertilizer components canbe obtained by regenerating the strong acid cation exchange resin with astrong acid such as hydrochloric acid or nitric acid to produce an acidstream rich in potassium salt. Ammonium-based fertilizer components canbe obtained by regenerating the anion ion exchange resin with a strongor weak base such as sodium or potassium hydroxide and ammoniumhydroxide to obtain an alkaline stream which is rich in nitrogen. Afterion exchange, the resulting sugar solution is concentrated to produce asyrup, which is crystallized twice to produce impure crystallized sugarand white strap molasses. Although the patent describes the productionof potassium and ammonium-based fertilizer components, there is nodiscussion of the recovery of inorganic salts arising from an acidicpretreatment and neutralization step.

U.S. Pat. No. 4,101,338 (Rapaport et al) disclose the separation ofsucrose from impurities in sugar cane molasses. Rapaport et al. teachthe pretreatment of a molasses stream to remove a significant amount oforganic non-carbohydrate impurities and colour. The pretreatment can becarried out by precipitation with iron salts, such as ferric chloride orferric sulfate. The insoluble flocculants are then removed from themolasses stream and the soluble iron salts are removed by the additionof lime and phosphoric acid or phosphate salts. The pretreatment mayalso be carried out by other processes which include: centrifugation,with removal of the cake; precipitation by adding ethanol to themolasses stream; and filtering the molasses across a membrane ofcellulose acetate. Regardless of the pretreatment process, the purposeis to decrease the amount of organic non-carbohydrate impurities so thata subsequent step of ion exclusion chromatography will separate thecarbohydrate fraction from the dissolved impurities. Rapaport et al.report that the pretreatment decreased the ash content to 10% and theorganic non-sugar content to 16.3% of the solids present.

Organic non-carbohydrate impurities, within a lignocellulosic system,cannot be removed by the methods of U.S. Pat. No. 4,101,338 (Rapaport etal.) According to Rapaport's method, the amount of solids precipitatedby iron salts or ethanol is modest and no solids are removed bycentrifugation. By contrast, the sugar streams produced during theprocessing of lignocellulosic feedstock have a much higher level oforganic non-carbohydrate impurities and inorganic salts. Rapaport et al.do not address the processing of such concentrated streams. Furthermore,the use of cellulose acetate membranes in a lignocellulosic system wouldnot be feasible since such membranes would be destroyed by cellulaseenzymes.

A process for the pretreatment, enzymatic hydrolysis and sugarfermentation of lignocellulosic feedstocks is required that addressesthe problems associated with high inorganic salt concentrations in thefeedstock and in the process. The development of such a process wouldrepresent a significant step forward in the commercialization of ethanolproduction from lignocellulosic biomass.

SUMMARY OF THE INVENTION

The present invention relates to a method for processing lignocellulosicfeedstocks. More specifically, the present invention provides a methodfor recovering inorganic salt during the processing of lignocellulosicfeedstocks.

It is an object of the invention to provide an improved method forrecovery of inorganic salt during processing of lignocellulosicfeedstocks.

According to the present invention, there is provided a method (A) forrecovering inorganic salt during processing of a lignocellulosicfeedstock comprising:

a. pretreating the lignocellulosic feedstock by adding one or more thanone acid to the lignocellulosic feedstock to produce a pretreatedlignocellulosic feedstock;

b. adding one or more than one soluble base to the pretreatedlignocellulosic feedstock to adjust the pretreated lignocellulosicfeedstock to a pH of about 4.0 to about 6.0 to produce a neutralizedfeedstock;

c. enzymatically hydrolyzing the neutralized feedstock to produce asugar stream and an enzyme hydrolyzed feedstock; and

d. recovering the inorganic salt from a stream produced from thelignocellulosic feedstock prior to the step of pretreating (step a.), astream obtained from the pretreated lignocellulosic feedstock, a streamobtained from the neutralized feedstock, the sugar stream, or acombination thereof.

The lignocellulosic feedstock used in the method as described above maybe selected from the group consisting of corn stover, wheat straw,barley straw, canola straw, rice straw, oat straw, soybean stover,grass, switch grass, miscanthus, cord grass, and reed canary grass,aspen wood, sawdust, bagasse and beet pulp. Preferably, thelignocellulosic feedstock contains from about 0.2% to about 4% (w/w)potassium.

The present invention also pertains to the method (A) described above,wherein, in the step of recovering (step d.), the inorganic salt isrecovered by ion exclusion. The step of recovering may be followed bycrystallization of the inorganic salt. The inorganic salt may compriseammonium sulfate salts, ammonium phosphate salts, potassium sulfatesalts, ammonium sulfite salts, potassium sulfite salts, sodium sulfatesalts, sodium sulfite salts, magnesium sulfate, ammonium chloride,potassium chloride, magnesium chloride or a mixture thereof. Preferably,the inorganic salt is soluble. The ammonium sulfite salts, sodiumsulfite salts, potassium sulfite salts, or a mixture thereof may beconverted to sulfate salts by oxidation before or after the step ofrecovering (step d.).

The present invention provides a method (A) as described above, whereinthe inorganic salt may be concentrated by evaporation, membranefiltration, or a combination thereof prior to recovery to produce aconcentrated solution comprising the inorganic salt. The concentratedsolution may be clarified by membrane filtration, plate and framefiltration, or centrifugation prior to recovery.

The present invention also provides a method (A) described above,wherein the step of pretreatment (step a.) comprises a method selectedfrom the group consisting of batch dilute acid hydrolysis, continuousdilute acid hydrolysis, steam explosion and extrusion.

The one or more than one acid may be selected from the group consistingof sulfuric acid, sulfurous acid, sulfur dioxide, phosphoric acid, and acombination thereof. The one or more than one soluble base may beselected from the group consisting of ammonia, ammonium hydroxide,potassium hydroxide and sodium hydroxide.

Furthermore, the present invention pertains to the method (A) asdescribed above, wherein the step of pretreating (step a.) is performedat a temperature from about 160° C. to about 280° C., at a pH from about0.4 to about 2.0 and/or for a period of time from about 0.1 to about 30minutes.

Furthermore, the present invention pertains to the method (A) describedabove further comprising the steps of:

e. fermenting the sugar stream to produce a fermentation brothcomprising ethanol; and

f. distilling the fermentation broth to produce concentrated ethanol andstill bottoms.

Optionally, the inorganic salt may be recovered from the still bottomsfollowed by purifying the inorganic salt. Prior to the step ofrecovering the inorganic salt from the still bottoms, the concentrationof the still bottoms may be increased by evaporation, membranefiltration, or a combination thereof, to produce concentrated stillbottoms, followed by a step of ion exclusion chromatography using asimulated moving bed (SMB) process. The concentrated still bottoms maybe clarified by microfiltration, plate and frame filtration orcentrifugation prior to the step of ion exclusion chromatography. Thestep of purifying the inorganic salt may comprise crystallization of theinorganic salt or electrodialysis, drying or agglomeration andgranulation.

The present invention provides the method (A) as described above,wherein prior to the step of pretreating (step a.), the lignocellulosicfeedstock is pressed, leached, or a combination thereof to produce aleachate and wherein the leachate is combined with one or more than onesoluble inorganic salt stream obtained from the pretreated feedstock,the neutralized feedstock, the sugar stream, or a combination thereof toproduce a combined salt stream.

Furthermore, the inorganic salt present in the combined salt stream maybe concentrated by evaporation, membrane filtration, or a combinationthereof to produce a concentrated salt solution. The concentrated saltsolution may be clarified to produce a clarified salt solution. Theinorganic salt may be recovered from the clarified salt solution by ionexclusion chromatography.

Furthermore, there is provided the method (A) as described, whereinafter the step of enzymatically hydrolyzing (step c.), the sugar streamis separated from the enzyme hydrolyzed feedstock to form a solidresidue and a sugar hydrolyzate stream. The inorganic salt may beconcentrated by evaporation, membrane filtration, or a combinationthereof.

The present invention also provides a method (A) as described, wherein,in the step of pretreating (step a.), at least a portion ofhemicellulose in the feedstock is hydrolyzed to produce one or more thanone sugar monomer selected from the group consisting of xylose,arabinose, mannose, galactose and a combination thereof. Furthermore, inthe step of enzymatically hydrolyzing (step c.), one or more than onecellulase enzyme may be added to the neutralized feedstock so that atleast a portion of cellulose in the neutralized feedstock is hydrolyzedto produce glucose.

The present invention also pertains to a method (B) for recoveringinorganic salt during processing of a lignocellulosic feedstockcomprising:

a. pretreating the lignocellulosic feedstock by adding one or more thanone acid to the lignocellulosic feedstock to produce a pretreatedlignocellulosic feedstock;

b. adding one or more than one soluble base to the pretreatedlignocellulosic feedstock to adjust the pretreated lignocellulosicfeedstock to a pH of about 4.0 to about 6.0 to produce a neutralizedfeedstock;

c. enzymatically hydrolyzing the neutralized feedstock to produce asugar stream and an enzyme hydrolyzed feedstock;

d. fermenting the sugar stream to produce a fermentation brothcomprising ethanol;

e. distilling the fermentation broth to produce concentrated ethanol andstill bottoms; and

f. recovering the inorganic salt from the still bottoms to produce arecovered inorganic salt.

There is provided the method (B) described above further comprising thesteps of purifying the recovered inorganic salt to obtain a purifiedinorganic salt and producing a product comprising the purified inorganicsalt. The step of purifying may comprise performing ion exclusionchromatography, followed by electrodialysis, drying, agglomeration andgranulation, or crystallization.

The present invention provides a process for the conversion of alignocellulosic feedstock to sugar, and optionally fermenting the sugarto ethanol. The process further involves the recovery of inorganic saltsformed during the conversion process and, optionally, the recovery ofsalts from the initial feedstock. The recovery of the inorganic salt maybe carried out by ion exclusion followed by electrodialysis, drying,agglomeration and granulation, or crystallization. The recoveredinorganic salts, which can include potassium sulfate salts, ammoniumsulfate salts, ammonium phosphate salts, sodium phosphate salts, sodiumsulfate, other salts, and mixtures of these salts, may be used for anydesired purpose, for example as a fertilizer.

The process of the present invention overcomes several disadvantages ofthe prior art by taking into account the difficulties in the conversionof lignocellulosic feedstocks to sugar and then ethanol. By removinginorganic salt during the processing of lignocellulosic feedstock,several of the steps operate more efficiently, for example enzymatichydrolysis, or fermentation of sugar to ethanol, as the inhibitoryeffect of the salt is reduced. Furthermore, the inorganic saltsrecovered during this process and the value generated from these saltshelp offset the cost associated with the use of these salts. Theinvention also allows for removing inorganic salts from the feedstock,which decreases the acid requirement and assists in overcoming anyadverse effect the feedstock salts can have on the conversion process.The present invention offers significant advances in the production ofsugar, ethanol, and other products from lignocellulosic feedstocks.

This summary of the invention does not necessarily describe all featuresof the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features of the invention will become more apparent fromthe following description in which reference is made to the appendeddrawings wherein:

FIG. 1 shows a schematic outline of the process of the presentinvention, and indicates several stages where inorganic salt may beremoved and recovered (indicated as stages 1-4).

DETAILED DESCRIPTION

The present invention relates to a method for processing lignocellulosicfeedstocks. More specifically, the present invention provides a methodfor recovering inorganic salt during the processing of lignocellulosicfeedstocks.

The following description is of a preferred embodiment.

The present invention provides a process for the recovery of inorganicsalt during the conversion of a lignocellulosic feedstock to sugar. Theinorganic salt may be used as fertilizer or for other purposes asdesired.

Therefore, the present invention provides a method (A) for recoveringinorganic salt during processing of a lignocellulosic feedstockcomprising:

a. pretreating the lignocellulosic feedstock by adding one or more thanone acid to the lignocellulosic feedstock to produce a pretreatedlignocellulosic feedstock;

b. adding one or more than one soluble base to the pretreatedlignocellulosic feedstock to adjust the pretreated lignocellulosicfeedstock to a pH of about 4.0 to about 6.0 to produce a neutralizedfeedstock;

c. enzymatically hydrolyzing the neutralized feedstock to produce asugar stream and an enzyme hydrolyzed feedstock; and

d. recovering the inorganic salt from a stream produced from thelignocellulosic feedstock prior to the step of pretreating (step a.), astream obtained from the pretreated lignocellulosic feedstock, a streamobtained from the neutralized feedstock, the sugar stream obtained fromthe enzyme hydrolyzed feedstock, or a combination thereof.

Additionally, the above method may comprise steps including:

e. fermenting the sugar stream to produce a fermentation brothcomprising ethanol; and

f. distilling the fermentation broth to produce concentrated ethanol andstill bottoms.

If desired, a salt stream may be recovered from the still bottoms (stepf) and combined with any inorganic salt obtained in step d, above.

The present invention also provides a method (B) for recoveringinorganic salt during processing of a lignocellulosic feedstockcomprising:

a. pretreating the lignocellulosic feedstock by adding one or more thanone acid, to the lignocellulosic feedstock to produce a pretreatedlignocellulosic feedstock;

b. adding one or more than one soluble base to the pretreatedlignocellulosic feedstock to adjust the pretreated lignocellulosicfeedstock to a pH of about 4.0 to about 6.0 to produce a neutralizedfeedstock;

c. enzymatically hydrolyzing the neutralized feedstock to produce asugar stream and an enzyme hydrolyzed feedstock;

d. fermenting the sugar stream to produce a fermentation brothcomprising ethanol;

e. distilling the fermentation broth to produce concentrated ethanol andstill bottoms; and

f. recovering the inorganic salt from the still bottoms to produce arecovered inorganic salt.

The feedstock for the process is a lignocellulosic material. By the term“lignocellulosic feedstock”, it is meant any type of plant biomass suchas but not limited to non-woody plant biomass, cultivated crops such as,but not limited to grasses, for example but not limited to C4 grasses,such as switch grass, cord grass, rye grass, miscanthus, reed canarygrass, or a combination thereof, or sugar processing residues such asbaggase, or beet pulp, agricultural residues, for example, soybeanstover, corn stover, rice straw, rice hulls, barley straw, corn cobs,wheat straw, canola straw, rice straw, oat straw, oat hulls, corn fiber,recycled wood pulp fiber, sawdust, hardwood, for example aspen wood andsawdust, softwood, or a combination thereof. Further, thelignocellulosic feedstock may comprise cellulosic waste material suchas, but not limited to newsprint, cardboard, sawdust and the like.Lignocellulosic feedstock may comprise one species of fiber oralternatively, lignocellulosic feedstock may comprise a mixture offibers that originate from different lignocellulosic feedstocks.Furthermore, the lignocellulosic feedstock may comprise freshlignocellulosic feedstock, partially dried lignocellulosic feedstock,fully dried lignocellulosic feedstock or a combination thereof.

Lignocellulosic feedstocks comprise cellulose in an amount greater thanabout 20%, more preferably greater than about 30%, still more preferablygreater than about 40% (w/w). The lignocellulosic feedstock alsocomprises lignin in an amount greater than about 10%, more preferably inan amount greater than about 15% (w/w). The lignocellulosic feedstockalso comprises a combined amount of sucrose, fructose and starch in anamount less than about 20%, preferably less than about 10% (w/w). Theweight percentages disclosed above are relative to the mass of thelignocellulosic feedstock as it exists prior to the step of adding (stepb., above).

By the term “inorganic salt”, it is meant salts that do not containeither a cation or an anion with carbon-hydrogen bonds. This term ismeant to exclude salts containing acetate anions, oxalate anions andother organic anions. These salts, and other salts containing an anionwith a carbon-hydrogen bond, are “organic salts”.

Preferably, the inorganic salt is soluble. By the term “solubleinorganic salt”, it is meant that the inorganic salt has a solubility inwater that is at least 0.1 M at 20° C. Calcium hydroxide, lime andcalcium sulfate are examples of insoluble inorganic salts.

Most lignocellulosic feedstocks contain 0.2% to 4% (w/w) potassium.Examples, which are not to be considered limiting in any manner, of theamount of potassium in several varieties of corn stover, barley straw,and wheat straw are shown in Table 1.

TABLE 1 2002 Lignocellulosic feedstock harvest potassium (% w/w) contentFeedstock Variety Location Potassium (%) Corn Stover Pioneer 33B51Nebraska 0.73 Corn Stover Pioneer 33P67 Nebraska 2.07 Corn Stover DekalbS3-32 Iowa 0.56 Corn Stover Dekalb 44-46 Iowa 0.44 Corn Stover Pioneer33P67 Iowa 2.02 Corn Stover Pioneer 36R11 Iowa 0.61 Corn Stover Pioneer36R11 Minnesota 1.01 Corn Stover NK 67T4 Iowa 1.72 Barley Straw ACLacombe Alberta 1.94 Barley Straw AC Lacombe Alberta 1.57 Barley StrawAC Metcalfe Alberta 2.22 Barley Straw AC Metcalfe Manitoba 1.24 WheatStraw Prodigy Alberta 1.37 Wheat Straw Prodigy Alberta 0.52 Wheat StrawSplendor Alberta 0.55 Wheat Straw Splendor Alberta 1.59 Wheat Straw CDCStratus Manitoba 0.82 Wheat Straw AC Barrie Manitoba 0.38 Wheat StrawCDC Stratus Manitoba 0.61 Wheat Straw AC Metcalf Manitoba 0.97 WheatStraw AC Barrie HRS Wheat Manitoba 0.44 Wheat Straw Durum Manitoba 0.86Wheat Straw HRS Wheat Manitoba 0.67 Wheat Straw Caphorn England 0.62Wheat Straw Gladiator England 0.95 Wheat Straw Histories England 0.67Wheat Straw Histories England 0.79 Wheat Straw Consort England 0.68Wheat Straw Consort England 1.12 Wheat Straw Consort England 1.14 WheatStraw Caphorn France 1.62 Wheat Straw Excellenz France 1.34 Wheat StrawGladiator France 1.73 Wheat Straw Caphorn France 1.16 Wheat StrawGladiator France 1.12

In addition to potassium, other common cationic elements inlignocellulosic feedstocks include magnesium, sodium and calcium. Themost prevalent inorganic anions are typically phosphate and chloride.The most prevalent inorganic salts may therefore include chloride andphosphate salts of potassium, magnesium, sodium and calcium. Organicsalts such as oxalates and acetates are also present in manylignocellulosic feedstocks.

The lignocellulosic feedstock for the process described hereinpreferably contains potassium. The higher the inorganic salt orpotassium concentration, the more beneficial the outcome of the processof the present invention. The presence of inorganic salts within thetreated lignocellulosic feedstock leads to the degradation of xylosethat is produced as a result of processing the lignocellulosicfeedstock. Degradation of xylose results in reduced yields of sugar,ethanol or a combination thereof. Furthermore, any inorganic salt, forexample potassium sulfate, that is recovered as a by-product during theprocessing of lignocellulosic feedstocks, may be used for a variety ofpurposes, for example within a fertilizer.

As a result of processing the lignocellulosic feedstock as describedherein, product streams are produced that contain sugar, inorganicsalts, organic salts and other by-products. The inorganic salt may berecovered from the product streams by ion exclusion or any othersuitable method as would be known to one of skill in the art.

By the term “ion-exchange”, it is meant a separation technique thatemploys a chemical reaction in which an ion from solution is exchangedfor a similarly charged ion attached to an immobile solid particle. Theion exchange resins may be cation exchangers that have positivelycharged mobile ions available for exchange, or anion exchangers, whoseexchangeable ions are negatively charged. The solid ion exchangeparticles may be either naturally occurring inorganic zeolites orsynthetically produced organic resins.

By the term “ion exclusion”, it is meant a separation technique thatseparates ionic species in solution from non-ionic species, or weaklyionic species from strongly ionic species, by employing a resin having astructure that allows the non-ionic species or weakly ionic species todiffuse into it while preventing more ionic species from entering theresin. The species with less ionic character then elutes after the moreionic species.

As used herein, the term “membrane filtration” refers to any process offiltering a solution with a membrane that is suitable for concentratinga solution. Included in this definition are microfiltration, whichemploys membranes of a pore size of 0.05-1 microns for the removal ofparticulate matter; ultrafiltration, which employs membranes with acut-off of 500-50,000 mw for removing large soluble molecules; andreverse osmosis using nanofiltration membranes to separate smallmolecules from water. The term “reverse osmosis” refers to theseparation of solutions having different solute concentrations with asemi-permeable membrane by applying sufficient pressure to the moreconcentrated liquid to reverse the direction of osmosis across themembrane. The term “nanofiltration” refers to processes that separatesolutions of differing solute concentrations using reverse osmosis, butthat employ membranes which are finer than those used in reverseosmosis.

In addition to concentrating a solution, microfiltration may be used forclarification.

Separation by ion exclusion may employ Simulated Moving Bed (SMB)technology. As used herein, the term “Simulated Moving Bed” or “SMB”refers to an ion exclusion chromatographic separation process thatutilizes a set of columns interconnected in series in which liquidcirculates in the unit by simultaneous shifting of the columns in theopposite direction. As used herein, this term encompasses ImprovedSimulated Moving Bed (ISMB) systems. A non-limiting example of an ISMBsystem is provided in Example 1. SMB is a preferred separation methodfor ion exclusion chromatography since solvent use is minimized, therebyleading to a greatly reduced cost of operation when compared totraditional batch chromatography methods.

Prior to separation by ion exclusion, the inorganic salt solution may beconcentrated and clarified. Concentration may be carried out byevaporation or by microfiltration (0.14 microns) to remove particles,ultrafiltration (500-2000 mw cut off) to remove soluble lignin and otherlarge molecules and reverse osmosis to increase solids to aconcentration of about 12 to about 20%, or any amount therebetween,followed by evaporation. Following concentration, the solution may beclarified by microfiltration, plate and frame filtration orcentrifugation.

After separation from the product stream, the inorganic salt may becrystallized, dried or subjected to electrodialysis or agglomeration andgranulation, and used as desired, for example as a solid fertilizer.Alternatively, the inorganic salt may be concentrated as a wet slurryand used in a liquid form, for example as a liquid fertilizer. Theremaining components within the product streams, for example sugar, maybe further processed or collected, as desired.

By the term “electrodialysis”, it is meant a separation process in whichions are transported across a semi-permeable membrane under theinfluence of an electric potential. The membrane may be either cation oranion selective to allow for the separation of cations or anions,respectively.

By the term “crystallization”, it is meant any process for the formationof solid particles or crystals of a solute from a saturated solution.This can be carried out by concentration, cooling (under vacuum or witha heat exchanger), reaction displacement or equilibrium displacement.

By the term “agglomeration and granulation”, it is meant process stepsto modify particle size, for example, to improve bulk properties.Non-limiting examples of bulk properties that can be improved include,but are not limited to, dissolving behavior, form and stability of thegranulated product and storage stability.

By the term “drying”, it is meant any process for removing water,volatile components or other liquids from a solid material, to reducethe content of residual liquid to an acceptable low value. Thisincludes, but is not limited to, direct and indirect drying. Directdrying refers to using direct contact of hot gases to drive off some, orall of the water, and indirect drying refers to contact with a heatedsurface as opposed to hot gas.

The inorganic salts in the product stream result from thelignocellulosic feedstock itself, and from the acids and bases usedduring the processing of the lignocellulosic feedstock. For example, theinorganic salt mixtures that arise from sulfuric acid include mixturesof sulfuric acid, sodium bisulfate, and disodium sulfate, depending onthe pH of the system and on the total ionic concentration. For thisdiscussion, these salt mixtures will be referred to as “sodium sulfatesalts”. Other salt mixtures may also be present in the product streamsfor example, but not limited to, ammonium sulfate salts (sulfuric acid,ammonium bisulfate, and diammonium sulfate); sodium sulfite salts,(sulfurous acid, sodium bisulfite, and disodium sulfite); ammoniumsulfite salts (sulfuric acid, ammonium bisulfite, and diammoniumsulfite), sodium phosphate salts (phosphoric acid, sodium dihydrogenphosphate, and disodium hydrogen phosphate), ammonium phosphate salts(phosphoric acid, diammonium hydrogen phosphate, and ammonium dihydrogenphosphate), potassium sulfate salts (sulfuric acid, potassium bisulfate,and dipotassium sulfate), potassium sulfite salts (sulfuric acid,potassium bisulfite, and dipotassium sulfite), and potassium phosphatesalts (phosphoric acid, potassium dihydrogen phosphate, and dipotassiumhydrogen phosphate).

The inorganic salts recovered from the process as described herein havevalue as a fertilizer; however, additional uses of the recovered saltsmay be exploited as desired. In the case of fertilizer, ammonium,potassium, sulfate, and phosphate salts are typically of value. Othercompounds present, including inorganic salts of sodium and sulfitesalts, may be of less value in fertilizer. However, these inorganicsalts can be converted to forms of higher value. For example, which isnot to be considered limiting, sodium salts can be converted topotassium salts by the use of ion exchange. In this example, sodiumhydroxide may be used for some or all of the neutralization of sulfuricacid during the processing of a lignocellulosic feedstock and the sodiumion exchanged with potassium using a cation exchange resin. Theresulting potassium salt may then be of more value as a fertilizer.

Additionally, sulfite salts can be converted to sulfate salts byoxidation with air or with oxidizing agents. For example, sulfurous acidor sulfur dioxide present in pretreatment may be used to oxidize thesulfite salts to sulfate for use in fertilizer.

The step of pretreatment increases the susceptibility of thelignocellulosic feedstock to hydrolysis by cellulase enzymes. Thepretreatment is carried out to hydrolyze the hemicellulose, or a portionthereof, that is present in the lignocellulosic feedstock to monomericsugars, for example xylose, arabinose, mannose, galactose, or acombination thereof. Preferably, the pretreatment is designed to carryout almost complete hydrolysis of the hemicellulose and a small amountof conversion of cellulose to glucose. The cellulose is hydrolyzed toglucose in a subsequent step that uses cellulase enzymes. During thepretreatment, typically a dilute acid, from about 0.02% (w/v) to about1% (w/v), or any amount therebetween, is used for the treatment of thelignocellulosic feedstock. The preferred acid for pretreatment issulfuric acid. Acid pretreatment is familiar to those skilled in theart, see for example U.S. Pat. No. 5,536,325 (Brink); U.S. Pat. No.4,237,226 (Grethlein; which are incorporated herein by reference). Othermethods that are known within the art may be used as required forpreparation of a pretreated feedstock, for example, but not limited to,those disclosed in U.S. Pat. No. 4,556,430 (Converse; which areincorporated herein by reference).

Preferably, the step of reacting the acidified feedstock is performed ata temperature between about 100° C. to about 280° C., or any amounttherebetween, for example a temperature of 100, 120, 140, 160, 180, 200,220, 240, 260, 280° C., or any amount therebetween, at a pH from aboutpH 0.4 to about pH 2.5 or any amount therebetween, for example, a pH of0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, or anyamount therebetween, for about 5 seconds to about 60 minutes, or anyamount therebetween, for example, for 5, 10, 20, 30, 40, 50, 60 seconds,or for 1.5, 2, 4, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60minutes, and any amount therebetween. It is understood by those skilledin the art that the feedstock temperature is that of the feedstockitself, which might differ from the temperature measured outside thereaction chamber. Devices used to carry out this pretreatment include,but are not limited to sealed batch reactors, continuous extruders andsteam guns.

A preferred pretreatment, without intending to be limiting, is steamexplosion described in U.S. Pat. No. 4,461,648 Foody; which isincorporated herein by reference). A typical set of pretreatmentconditions for processing lignocellulosic feedstocks is a temperature ofabout 170° C. to about 260° C., for a period of about 0.1 to about 30minutes and/or at a pH of about 0.4 to about 2.0.

It is also within the scope of the present invention that a two-stagepretreatment process may be used, whereby the first stage improves thecellulose hydrolysis somewhat while solubilizing primarily thehemicellulose but little cellulose. The second stage then completes afull pretreatment. Using this method, the first stage reaction is run ata temperature of less than about 180° C. while the second stage reactionis run at a temperature of greater than about 180° C. Preferably, thefirst stage of the reaction is carried out at a temperature of about 60°C. to about 140° C., or an amount therebetween, for 0.25 to 24 hours, orany amount therebetween, and at a pH from about pH 0.5 to about pH 2.5,or any amount therebetween. More preferably, the first stage ofpretreatment is carried out at a temperature of 100° C. to 130° C. for0.5 to 3 hours at pH 0.5 to 2.5. While the second stage of reaction maybe carried out at a temperature of 180° C. to 270° C., at pH 0.5 to 2.5for a period of 5 seconds to 120 seconds. The two-stage pretreatmentprovides separate recovery of the soluble monomers from hemicellulosefor downstream processing.

Furthermore, the lignocellulosic feedstock may be processed using themethods disclosed in WO 02/070753 (Griffin et al., which is incorporatedherein by reference). A pretreatment process using flow-throughhydrolysis is disclosed in U.S. Pat. No. 4,237,226 (Grethlein et al.,which is incorporated herein by reference).

The low pH for acidic chemical treatments requires the addition of acidto the lignocellulosic feedstock. Any acid can be used to adjust the pHof the lignocellulosic feedstock. However, preferred acids are sulfuricacid, sulfurous acid, sulfur dioxide, and phosphoric acid, due to theirlow cost, effectiveness in pretreatment, and, in the case of sulfate andphosphate salts, their further use within a fertilizer. A suitablealternative to sulfuric acid is phosphoric acid.

The pretreated lignocellulosic feedstock may be processed to remove anyinorganic salt present prior to addition of the soluble base to thelignocellulosic feedstock. For example, the pretreated feedstock may bewashed to remove the sugar-acid mixture from the solids portion. Theseparated acid stream may then be neutralized and processed as describedbelow for sugar fermentation or added into a sugar stream from theenzyme hydrolysis for fermentation. Alternatively, the pretreatedfeedstock may be washed to remove the sugar-acid mixture from the solidsportion, and the wash stream treated with base prior to separating theinorganic salt from the sugar in the salt stream. After salt removal,the neutralized wash stream may be processed for sugar fermentation orenzymatic hydrolysis, as described below. The inorganic salt recoveredfrom the wash stream obtained from the pretreated lignocellulosicfeedstock may be concentrated, or dried as described herein.

The pretreated lignocellulosic feedstock is highly acidic. It isneutralized prior to enzymatic hydrolysis and sugar fermentation.Cellulase enzymes are active over a range of pH of about 3 to about 7,or any range therebetween, preferably, the pH is from about 4.0 to about6.0, or any range therebetween, and more preferably the pH is from about4.5 to about 5.0, or any range therebetween. For example, the pH is 3.0,3.5, 3.7, 4.0, 4.2, 4.5, 4.7, 5.0, 5.2, 5.5, 6.0, 6.5, 7.0, or anyamount therebetween. Yeast and Zymomonas bacteria are typically used forsugar fermentation. The optimum pH for yeast is from about pH 4 to aboutpH 5, while the optimum pH for Zymomonas is from about pH 5 to about pH6. In principle, any soluble base can be used to adjust the pH of acidicmaterial. However, it is preferred that the base used for pH adjustmentof acid material is ammonia gas or ammonia dissolved in water forexample, ammonium hydroxide. Sodium hydroxide or potassium hydroxide mayalso be used. These compounds are inexpensive, effective, and, in thecase of ammonium and potassium salts, of high value if the inorganicsalt is to be used in fertilizer.

By the term “soluble base”, it is meant a base that has a solubility inwater that is at least 0.1 M at 20° C. This term is meant to excludesalts that are slightly soluble or insoluble. Examples of bases that areexcluded are CaCO₃ and Ca(OH)₂. Insoluble bases cannot be recoveredaccording to the methods of the present invention. The term “base” ismeant to encompass any species that, when dissolved in water, gives asolution with a pH that is more than 7.

Following the addition of the soluble base, enzymatic hydrolysis iscarried out. Typically, the enzymes used for hydrolysis are cellulaseenzymes that hydrolyze the cellulose to glucose. Any cellulase may beused, however, preferred cellulase enzymes are those made by the fungusTrichoderma. Preferably, the enzyme treatment is carried out betweenabout 40° C. to about 60° C., or any temperature range therebetween, orbetween about 45° C. and about 55° C., or any temperature rangetherebetween. For example the enzyme treatment may be carried out at 40,42, 44, 46, 48, 50, 52, 54, 56, 58, 60° C., or any amount therebetween.The treatment may be performed for a time period of about 1 to about 10days, or any time interval therebetween, or for a time period of about 3to about 7 days, or any time interval therebetween. For example, thetreatment may be performed for a time period of 1, 2, 3, 4, 5, 6, 7, 8,9 or 10 days, or any amount therebetween.

Following enzymatic hydrolysis, the aqueous phase containing the sugar,inorganic salts, and other soluble compounds may be separated from theinsoluble, un-hydrolyzed solids phase to produce a soluble sugar stream(also referred to as the wash stream). The un-hydrolyzed solids areprimarily lignin and cellulose, and, to a lesser extent, silica,insoluble salts and other compounds. The sugar stream can be pumped,mixed, and controlled more easily than a slurry containing liquids andinsoluble solids. The insoluble solids are separated from the sugarstream by any suitable method, for example but not limited to plate andframe filtration, crossflow filtration, centrifugation, or other methodsknown to one of skill in the art.

Sugars present in the sugar stream, for example glucose, xylose,arabinose, mannose, galactose, or mixtures thereof, may be fermented bymicrobes. The fermentation products can include any desired productsthat generate value to the fermentation plant. The preferredfermentation products are ethanol and lactic acid, both of which havelarge markets and are made efficiently by many microbes. For ethanolproduction, fermentation can be carried out by one or more than onemicrobe that is able to ferment the sugars to ethanol. For example, thefermentation may be carried out by recombinant Saccharomyces yeast thathas been engineered to ferment glucose, mannose, galactose and xylose toethanol, or glucose, mannose, galactose, xylose, and arabinose toethanol. Recombinant yeasts that can ferment xylose to ethanol aredescribed in U.S. Pat. No. 5,789,210 (the contents of which are hereinincorporated by reference). The yeast produces a fermentation brothcomprising ethanol in an aqueous solution. For lactic acid production,the fermentation can be carried out by one or more than one microbe thatferments the sugars to lactic acid.

If ethanol is the product, the ethanol may then be recovered from thefermentation broth. For example, the ethanol may be recovered bydistillation of the fermentation broth. After recovery of the ethanol,for example by distillation, further ethanol purification may be carriedout by adsorption or other methods familiar to one of skill in the art.The aqueous stream after distillation is still and contains yeast cells,inorganic salts, unfermented sugars, organic salts and other impurities.

Inorganic salts present in the still bottoms may also be recovered usingany suitable method known to one of skill in the art, for example, butnot limited to ion exclusion. These processes can be followed bycrystallization, electrodialysis, drying, or agglomeration andgranulation. A preferred method for recovering the inorganic salt fromthe still bottoms is increasing the concentration of the still bottomsby evaporation, membrane filtration, or a combination thereof, followedby clarification by microfiltration, plate and frame filtration andcentrifugation. This is followed by ion exclusion chromatography using asimulated moving bed (SMB) process and then crystallization,electrodialysis, drying, or agglomeration and granulation.

Inorganic salts may also be removed from the lignocellulosic feedstockprior to pretreatment by washing, leaching, or a combination thereof toproduce a liquid stream or “leachate”. An example of a leaching processis described in WO 02/070753 (Griffin et al., which is incorporatedherein by reference). This process involves contacting thelignocellulosic feedstock with water for two minutes or longer, and thenseparating the solids from the aqueous phase. This decreases the acidrequirement for pretreatment, and decreases costs, and degradation ofxylose, in the pretreatment process.

After leaching, the aqueous solution containing salts (the “leachate”)contains potassium and other salts and trace elements that may be ofvalue for subsequent use, for example within a fertilizer. The leachatemay be concentrated by evaporation or filtered through a reverse osmosismembrane to remove the water or subjected to reverse osmosis andevaporation. The leachate may be subsequently clarified bymicrofiltration, plate and frame filtration or centrifugation. Leachatesalts can be separated from organics by ion exclusion chromatographyusing a simulated moving bed (SMB) process to produce a product that isuseable as a fertilizer. Either the liquid or the solid salt streamsobtained from the leachate can be combined with other salt streamsproduced as described herein.

With reference to FIG. 1, there is shown an outline of the method of thepresent invention for the processing of lignocellulosic feedstock (100)to sugar (300, 400) and ethanol (600), through the successive processesof pretreatment (200), enzymatic hydrolysis (300), sugar fermentation(400), and ethanol recovery (500). As indicated in this figure, thereare several steps leading to the production of ethanol where inorganicsalt may be removed. For example, which is not to be consideredlimiting, inorganic salt may be removed at the stages indicated as 1, 2,3, and 4 (150, 250, 350 and 550, respectively) in FIG. 1.

Following pretreatment with acid (200; FIG. 1), the lignocellulosicfeedstock may be washed with water (250) to remove the inorganic saltsat step 1. Prior to pretreatment, the acid, for example sulfuric acid,sulfurous acid, sulfur dioxide, or phosphoric acid, is added to thelignocellulosic feedstock to adjust the pH, for example, to about 0.4 toabout 2.0, as described above. After pretreatment (200), thelignocellulosic feedstock is neutralized to a pH, for example, of about4 to about 6 for example using ammonia or other alkali, as describedabove. The resulting inorganic salt can then be removed from thelignocellulosic feedstock at step 2 (250). The separation is carried outoptionally by adding water to the pretreated lignocellulosic feedstock(200) and then separating the aqueous phase from the solids using afilter press, centrifuge or other suitable equipment. The aqueous stream(soluble stream) at this point is known as the pentose washings. Thesolids concentration in the pentose washings can be increased byevaporation, membrane filtration or a combination thereof.

The pentose washings containing ammonium sulfate and other inorganicsalts can not be crystallized without further processing to remove theorganic impurities. Ion exclusion by SMB chromatography can be used toseparate the inorganic salts from the organic impurities. The inorganicsalts can then be purified by crystallization or electrodialysis,drying, or agglomeration and granulation. The salt stream can then beused as a liquid fertilizer, or alternately dried and used as a solidfertilizer.

The resulting salt stream obtained following pretreatment of thelignocellulosic feedstock, either comprising sugars, or followingremoval of sugars, can be sold separately or combined with other saltstreams obtained in the process described herein. For example, eitherthe liquid or the solid salt streams obtained from the pentose washingscan be combined with the salts from the leachate, indicated as step 1 inFIG. 1 (150), described above.

Preferably, the desalted sugar streams (pentose washings) are fermentedto ethanol, since the desalted streams are easier to ferment than thestreams containing salt.

The present invention also contemplates separating the aqueous salt andsugar stream from the un-hydrolyzed, insoluble solids following theenzymatic hydrolysis (300) at step 3 (350). The process for recovery ofinorganic salts following enzymatic hydrolysis (300) at step 3 (350) isanalogous to the process of salt recovery described above forpretreatment (200), at step 1 (150). For example, the wash streamobtained at step 3 (350) may be concentrated, or the sugars present inthe wash stream obtained at step 3 removed and the remaining salt streamconcentrated, and the sugar stream collected, or further processed at400 (sugar fermentation) to produce ethanol.

The hydrolyzate stream produced following enzymatic hydrolysis (300),and containing salt and sugars is sent to fermentation (400), whereyeast or other suitable microbes ferment the sugar to ethanol (600) orother products. If ethanol is made, it is recovered by distillation orother suitable means (500). The remaining slurry is the still bottoms(700) and contains unfermented sugars, inorganic salts, organic salts,yeast cells, and other compounds. The inorganic salts can be recoveredfrom the still bottoms by means described above, and then used asdesired, for example as a fertilizer.

Also shown in FIG. 1, is the removal of inorganic salts from thelignocellulosic feedstock prior to pretreatment (100) at step 1 (150).This may be carried out by leaching or other process, as describedabove.

The present invention may be illustrated in the following examples.However, it is to be understood that these examples are for illustrativepurposes only, and should not be used to limit the scope of the presentinvention in any manner.

EXAMPLES Example 1 Recovery of Soluble Inorganic Salt from a HydrolyzateSugar Stream

A sugar hydrolyzate stream containing sodium sulfate and other solubleinorganic salts was prepared as follows.

Feedstock Preparation

Wheat straw was received in bales measuring 3 feet by 3 feet by 4 feet.The wheat straw consisted of 60.3% carbohydrates, 18.7% lignin, 3.6%protein, 3.1% silica, and 4.9% non-silica inorganic salts. The inorganicsalts included the cationic salt ions potassium (1.2%), calcium (0.57%),sodium (0.04%) and magnesium (0.15%), and the anionic ions chloride(0.22%) and phosphate (0.04%). The organic salt oxalate was also presentat a concentration of 0.51%.

Two batches of 15 tonnes of the straw were hammer-milled to an averagesize of ⅛″ and slurried in water at a ratio of 10 parts water to 1 partsolids. The slurry was pumped through piping heated by direct injectionwith 350 psig steam to reach a temperature of 185° C. Once at thistemperature, 10% sulfuric acid was added to reach a level of 0.9% acidon solids (w/w). The heated, acidified stock was held at this conditionfor 2 minutes as it passed through a pipe of 8 inches diameter. Uponexiting the pipe, the slurry was flashed through a series of threecyclones to drop the temperature to 70° C. and adjusted to pH 5.0 with30% concentrated sodium hydroxide. The slurry was finally cooled to 50°C. by passing it through a heat exchanger cooled with cold water.

Upon acid addition, the soluble inorganic salts of potassium sulfate,sodium sulfate, and magnesium sulfate were formed. The insoluble salt,calcium sulfate, was also formed. Upon neutralization with sodiumhydroxide, which is soluble, the concentration of sodium sulfate in theslurry increased markedly. The calcium sulfate concentration was abovethe solubility limit and a portion of it precipitated and deposited onthe cyclones and related piping. A portion of the organic salt calciumoxalate also deposited on the equipment.

Hydrolysis

The neutralized, cooled pretreated slurry was then pumped into threehydrolysis tanks, each of working volume of about 130,000 liters. Thetanks are equipped with bottom-mounted eductors to mix the slurry; oneof the three tanks has two side-mounted agitators. The slurry consistedof 4.5% undissolved solids, and the undissolved solids consisted of 55%cellulose. Once the hydrolysis tanks were filled or the pretreatedslurry was exhausted, cellulase enzyme from Trichoderma reesei wasadded. The enzyme dosage was 25 mg protein per gram cellulose, whichcorresponded to a cellulase activity of 25.4 Filter Paper Units (FPU)per gram of cellulose.

The hydrolyses ran for 5 days, at which point over 90% of the cellulosewas converted to glucose. The final glucose concentration was 26.0 to28.0 g/L, with an average of 27.5 g/L. The hydrolysis slurries werepumped to a Lasta plate and frame filter press to separate theun-hydrolyzed solid residue from the aqueous stream. A polymericflocculent was added in line at a level of 1-3 kg polymer/t solids toimprove the rate of filtration. The filter cake was 45% solids. Theun-hydrolyzed solid residue contains primarily lignin and un-hydrolyzedcellulose, but also the insoluble salts such as calcium sulfate. Theaqueous process stream is essentially free of insoluble particles andcontains glucose, xylose, and arabinose sugar; the soluble salts sodiumsulfate, potassium sulfate, magnesium sulfate, and a small amount ofdissolved calcium sulfate; and acetic acid and other dissolved organics.

The process stream was evaporated under vacuum using a four-effectevaporator at 90° C., 80° C., 70° C. and 45° C., respectively, to avolume of 81,700 liters with a solids concentration of 34%. Some of theacetic acid evaporated with the water, and some solids precipitated uponevaporation. The pH of the evaporated slurry was adjusted to pH 6.5 with50% sodium hydroxide solution, and this caused more precipitation. Theconcentrated, pH-adjusted stream was sent to the Lasta plate and framefilter press a second time, with a Perlite filter aid, to remove theprecipitated solids. The clear, evaporated process stream had inorganicsalt concentrations of 105 g/L sodium sulfate, 40 g/L potassium sulfate,and 5 g/L magnesium sulfate. In addition, organic compounds presentincluded 153 g/L glucose, 49 g/L xylose, 7.3 g/L arabinose, 3.4 g/Lfurfural, 3.5 g/L hydroxymethyl furfural, and 9.1 g/L acetate salt, anorganic salt that was measured as acetic acid, and various trace metals(including trace quantities of calcium), and a significant amount ofunidentified impurities.

Ion Exclusion Chromatography

The inorganic, soluble salts sodium sulfate, potassium sulfate, andmagnesium sulfate were recovered from the concentrated process stream byion exclusion chromatography, as follows.

The ion exclusion chromatography separation was carried out over a15-day period with continuous operation except for periodic shutdownsfor filter changes and one complete cycle of water flushing. Theseparation was carried out on an Improved Simulated Moving Bed (ISMB)system (Eurodia Industrie S.A. of Wissous, France, available throughAmeridia, Somerset, N.J.) of volume 6700 liters, packed with cationexchange resin from Mitsubishi Chemical, resin #UBK530. The ISMB systemconsists of 4 columns with 4 bed shifts per cycle and was operated withthe feed stream at pH 5.8 to 6.5. The system was maintained at 70° C. aswas the process feed and the dilution water. The process stream was fedat an average rate of 262 liters per hour and dilution water was addedat a rate of 969 L/hr, which is an average ratio of 3.7:1 with theprocess feed. Salt raffinate and sugar product streams were collected ataverage flow rates of 760 and 461 liters/hr, respectively.

The salt raffinate stream contained over 99% of the salt. The inorganicsalt concentrations were 35.6 g/L sodium sulfate, 14.4 g/L potassiumsulfate, 1.9 g/L magnesium sulfate. In addition, the organic saltacetate was present at a concentration of 3.3 g/L, measured as aceticacid. A very small fraction of the organic compounds were present inthis stream at concentrations of 1.2 g/L glucose, 0.5 g/L xylose, 0.2g/L arabinose, 0.3 g/L furfural and 0.6 g/L hydroxymethyl furfural.

The sugar product stream contained the vast majority of the organiccompounds and tiny amounts of salt. The concentrations of this streamwere 1.2 g/L sodium sulfate, 0.4 g/L potassium sulfate, 66 g/L glucose,22 g/L xylose, 3.3 g/L arabinose, and 0.09 g/L acetic acid, measured asacetate salt.

The salt raffinate stream is evaporated to 40% solids, then sent to anevaporator-crystallizer to produce granulates for use as fertilizer.

Example 2 Recovery of Soluble Inorganic Salt from Wheat Straw Leachate

Wheat straw was received in bales measuring 3 feet by 3 feet by 4 feet.The wheat straw consisted of 15.9% moisture. The composition of thestraw, on a dry basis, was 60.1% carbohydrates, 19.7% lignin, 3.36%protein, 3.0% silica, and 4.5% non-silica salts. The inorganic cationicsalt ions included 1.28% potassium, 0.45% calcium, 0.04% sodium, and0.15% magnesium. The inorganic anions were chloride at 0.22% and 0.04%phosphate. The organic salt oxalate was present at a concentration of0.55%. A weight of 1199 kg wet straw was hammer-milled to ⅛ inch.

The hammer-milled straw was slurried in 49,590 liters of 65° C. water.The slurry was gravity fed into a mixed tank, where it was mixedovernight for 18 hours and maintained at 65° C. The pH was 6.4throughout the leaching process. The slurry was then flowed throughscreened baskets by gravity to separate the solids from the liquidleachate stream. The screened baskets produced a cake of 21.1% solidscontent.

The leachate contained 9.9% of the initial fiber solids. This was at aconcentration of 2010 mg/L total dissolved solids, which included 127mg/L protein, 262 mg/L potassium, 1.5 mg/L calcium, 36 mg/L magnesium,55 mg/L chloride and a majority of 1530 mg/L unidentified. Other thancalcium, which was not removed to a significant degree, the salts wereremoved from the straw by leaching at a yield of 87% to 93%. The proteinyield in the leachate was 14%.

The leachate stream was evaporated to increase the solids concentrationapproximately 100-fold, to a solids concentration of 19.9% and a volumeof 464 liters. A significant amount of protein precipitated and wasremoved by filtration. A preliminary evaluation of drying andcrystallizing the filtrate indicated that the inorganic saltsconstituted much too small a proportion of the total solids forcrystallization of the salts to be possible.

An aliquot of the leachate stream is fed to a laboratory ion exclusionchromatography system to separate the salts from the organics. The ionexclusion chromatography separation is carried out on a fixed bed ofvolume 127 mL, packed with cation exchange resin from MitsubishiChemical, resin #UBK530. The bed is operated with the feed stream at pH6.8. The column is maintained at 70° C. as is the feed and the elutionwater. Prior to carrying out the separation, the column is conditionedwith three bed volumes of the process stream. The process stream is fedin a pulse of 5 mL and elution water is then added at a rate of 4mL/minute. Salt raffinate and sugar product streams are collected as theconductivity of the effluent indicates the presence and absence of salt,respectively.

The salt raffinate stream contains most of the inorganic salts, whichare primarily potassium chloride and magnesium chloride and a smallamount of organic impurities. The inorganic salt concentrations are highenough to permit crystallization to recover the salts.

Example 3 Recovery of Soluble Inorganic Salts from Wheat Straw Leachate

Wheat straw was received in bales measuring 3 feet by 3 feet by 4 feet.The wheat straw consisted of 6.4% moisture. The composition of thestraw, on a dry basis, was 60.3% carbohydrates, 18.7% lignin, 3.6%protein, 3.1% silica, and 4.9% non-silica salts. The inorganic cationicsalt ions present included 1.22% potassium, 0.57% calcium, 0.04% sodium,and 0.15% magnesium. The inorganic anions were chloride at 0.10%, 0.16%phosphate and 0.08% sulfate. A weight of 3,363 kg of moist straw washammer-milled to ⅛ inch pieces. The hammer-milled straw was slurried in70,626 liters of 65° C. water. The slurry was gravity fed into a mixedtank, where it was mixed overnight for 18 hours and maintained at 65° C.The pH was 4.9 throughout the leaching process. The slurry was thenflowed through a centrifuge to separate the solids from the liquidleachate stream. The centrifuge produced a cake of 29.6% solids content.

The leachate contained 10.6% of the initial fiber solids. This was at aconcentration of 4090 mg/L total dissolved solids, which included 1138mg/L protein, 494 mg/L potassium, 67 mg/L calcium, 36 mg/L magnesium, 67mg/L chloride, 80 mg/L of sulfate, 45 mg/L of phosphate, 27 mg/L ofsodium, 163 mg/L of silica, 2010 mg/L of soluble phenolics and about 600mg/L unidentified. Other than calcium and silica, which were not removedto a significant degree, the salts were removed from the straw byleaching at a yield of 50% to 93%. The protein yield in the leachate was72%.

The leachate stream is evaporated to increase the solids concentrationapproximately 40-fold, to a solids concentration of 19.6% and a volumeof 1770 liters. A significant amount of protein precipitates and isremoved by filtration.

An aliquot of the leachate stream is fed to a laboratory ion exclusionchromatography system to separate the salts from the organics. The ionexclusion chromatography separation is carried out on a fixed bed ofvolume 127 mL, packed with cation exchange resin from MitsubishiChemical, resin #UBK530. The bed is operated with the feed stream at pH6.8. The column is maintained at 70° C. as is the feed and the elutionwater. Prior to carrying out the separation, the column is conditionedwith three bed volumes of the process stream. The process stream is fedin a pulse of 5 mL and elution water is then added at a rate of 4mL/minute. Salt raffinate and sugar product streams are collected as theconductivity of the effluent indicates the presence of salt and water,respectively.

The salt raffinate stream contains most of the inorganic salts, whichare primarily potassium chloride and magnesium chloride, and a smallamount of organic impurities. The inorganic salt concentrations are highenough to permit crystallization to recover the salts.

Example 4 Recovery of Soluble Inorganic Salts During Conversion of WheatStraw to Ethanol

A sugar hydrolyzate stream containing ammonium sulfate and other solubleinorganic salts was prepared as follows.

Wheat straw was received in bales measuring 3 feet by 3 feet by 4 feetand chopped and leached according to the procedures of Example 3. Theleached wheat straw consisted of 57.1% carbohydrates, 36.6% lignin,1.75% protein, 3.9% silica, and 0.8% non-silica salts. The saltsincluded 0.2% potassium, 0.17% calcium, 0.05% sodium, 0.03% magnesium,<0.01% phosphate, 0.014% chloride and 0.023% sulfate. The leached strawwas slurried in water at a ratio of 8 parts water to 1 part solids. Theslurry was pumped through piping heated by direct injection with 350psig steam to reach a temperature of 185° C. Once at this temperature,10% concentrated sulfuric acid was added at a level of 0.9% acid onsolids (w/w). The heated, acidified stock was held at this condition for2 minutes as it passed through a pipe of 8 inches diameter. Upon exitingthe pipe, the slurry was flashed through a series of three cyclones todrop the temperature to 75° C. and then cooled to 50° C. by using heatexchange with cool water. The slurry was then adjusted to pH 5.0 withconcentrated ammonium hydroxide.

Upon acid addition, the soluble salts of potassium sulfate, sodiumsulfate, and magnesium sulfate were formed. The insoluble salt, calciumsulfate, was also formed. Upon neutralization with ammonium hydroxide,which is soluble, the concentration of ammonium sulfate in the slurryincreased markedly. The calcium sulfate concentration was above thesolubility limit and a portion of it precipitated and deposited on thecyclones and related piping.

The neutralized, cooled pretreated slurry was then pumped into ahydrolysis tank at a volume of about 100,000 liters. The tank isequipped with side-mounted eductors to mix the slurry. The slurryconsisted of 4.5% undissolved solids, and the undissolved solidsconsisted of 55% cellulose. Once the pretreated slurry was added to thehydrolysis tank, cellulase enzyme from Trichoderma reesei was added. Theenzyme dosage was 35 mg protein per gram cellulose, which correspondedto a cellulase activity of 35.6 Filter Paper Units (FPU) per gram ofcellulose.

The hydrolysis ran for 2 days, at which point over 90% of the cellulosewas converted to glucose. The final glucose concentration was 26.0 to28.0 g/L, with an average of 27.5 g/L. The hydrolysis slurry was pumpedto a Lasta plate and frame filter press to separate the unhydrolyzedsolid residue from the aqueous stream. A polyacrylamide flocculent wasadded at a level of 1-3 kg/t solids to aid in the filtration. Theunhydrolyzed solid residue contains primarily lignin, unhydrolyzedcellulose and sand, but also the insoluble salts such as calciumsulfate. The aqueous process stream is essentially free of insolubleparticles and contains glucose, xylose, and arabinose sugar; the solublesalts ammonium sulfate, potassium sulfate, magnesium sulfate and a smallamount of dissolved calcium sulfate, and acetic acid, soluble lignin,and other dissolved organics.

The process stream was evaporated to increase the solids concentrationthree-fold by using a 4-effect falling film evaporator. The glucoseconcentration in the evaporated stream was 62 g/L, the xylose was 20g/L, and the acetic acid was 2.0 g/L. The evaporated stream was filteredacross the Lasta press with a Perlite filter aid to remove particulates.

The evaporated stream was pumped to a fermentor to carry out sugarfermentation with yeast. The yeast strain was LNHST from PurdueUniversity and has been genetically modified to enable it to fermentxylose, as well as glucose, to ethanol. The strain was grown bypropagation through successive fermentors, as described in U.S. Pat. No.5,789,210. The fermentation was fed over a period of 7 hours and thenrun as a batch for 48 hours at a volume of 65,000 liters.

At the conclusion of the fermentation, the yeast cells were removed bycentrifugation. The dilute beer was distilled to separate the ethanolfrom the aqueous solution. The distillation was carried out using a beercolumn and a rectifying column. The still bottoms were collected as aliquid stream from the bottom of the beer column with a volume of 87,000liters.

The still bottoms were evaporated under vacuum at 80° C. to a volume of18,000 liters with a solids concentration of 13%. Some of the solidsprecipitated upon evaporation. The pH of the evaporated slurry wasadjusted to pH 7.0 with 30% ammonium hydroxide solution, and this causedmore precipitation. The concentrated, pH-adjusted stream was sent to theLasta press with a diatomaceous earth body feed to remove theprecipitated solids. The clear, evaporated process stream had inorganicsalt concentrations of 55 g/L ammonium sulfate, 20 g/L potassiumsulfate, and 2.5 g/L magnesium sulfate. In addition, organic compoundspresent included 24 g/L xylose, 3.3 g/L arabinose, 3.4 g/L furfural, 3.5g/L hydroxymethyl furfural, and 9.1 g/L acetate salt, an organic saltthat was measured as acetic acid, and various trace metals (includingtrace quantities of calcium), and a significant amount of unidentifiedimpurities.

The inorganic, soluble salts ammonium sulfate, potassium sulfate, andmagnesium sulfate were recovered from the concentrated process stream byion exclusion chromatography, as follows.

The ion exclusion chromatography separation is carried out over a2.5-day period with continuous operation except for periodic shutdownsfor filter changes and one complete cycle of water flushing. Theseparation is carried out on an Improved Simulated Moving Bed (ISMB)system (Eurodia Industrie S.A. of Wissous, France, available throughAmeridia, Somerset, N.J.) of volume 6700 liters, packed with cationexchange resin from Mitsubishi Chemical, resin #UBK530. The ISMB systemconsists of 4 columns with 4 bed shifts per cycle and is operated withthe feed stream at pH 6.0 to 7.5. The system is maintained at 65° C. aswas the process feed and the dilution water. The process stream is fedat an average rate of 320 liters per hour and dilution water was addedat a rate of 960 L/hr, which is an average ratio of 3.0:1 with theprocess feed. Salt raffinate and sugar product streams are eachcollected at average flow rates of 640 liters/hr.

The salt raffinate stream contains over 99% of the salt. The inorganicsalt concentrations are 15.6 g/L ammonium sulfate, 4.4 g/L potassiumsulfate, and 1.9 g/L magnesium sulfate. In addition, the organic saltacetate is present at a concentration of 0.9 g/L, measured as aceticacid. A very small fraction of the organic compounds were in this streamat concentrations of 0.5 g/L xylose, 0.2 g/L arabinose, 0.3 g/Lfurfural, and 0.6 g/L hydroxymethyl furfural.

The sugar product stream contained the vast majority of the organiccompounds and very small amounts of salt. The concentrations of thisstream were 1.2 g/L ammonium sulfate, 0.4 g/L potassium sulfate, 14 g/Lxylose, 2.3 g/L arabinose, and 0.09 g/L acetic acid, measured as acetatesalt.

The salt raffinate stream is evaporated to 40% solids, then sent to anevaporator-crystallizer to produce granulates for use as fertilizer.

All citations are hereby incorporated by reference.

The present invention has been described with regard to one or moreembodiments. However, it will be apparent to persons skilled in the artthat a number of variations and modifications can be made withoutdeparting from the scope of the invention as defined in the claims.

REFERENCES

-   Thompson, D., Shaw, P. G. and Lacey, J. A. (2003) Post-Harvest    Processing Methods for Reduction of Silica and Alkali Metals in    Wheat Straw In Applied Biochemistry and Biotechnology    105-108:205-218.-   Wooley, R., Ruth, M., Sheehan, J., Ibsen, K., Majdeski, H. and    Galvez, A. (1999) Lignocellulosic Biomass to Ethanol Process Design    and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and    Enzyme Hydrolysis Current and Future Scenarios, Technical Report,    National Renewable Energy Laboratory pp. 16-17.

1. A method for recovering inorganic salt during processing of alignocellulosic feedstock comprising: a. pretreating the lignocellulosicfeedstock by adding one or more than one acid to the lignocellulosicfeedstock to produce a pretreated lignocellulosic feedstock; b. addingone or more than one soluble base to the pretreated lignocellulosicfeedstock to adjust the pretreated lignocellulosic feedstock to a pH ofabout 4.0 to about 6.0 to produce a neutralized feedstock; c.enzymatically hydrolyzing the neutralized feedstock to produce a sugarstream and an enzyme hydrolyzed feedstock; and d. recovering theinorganic salt from a stream produced from the lignocellulosic feedstockprior to the step of pretreating (step a.), a stream obtained from thepretreated lignocellulosic feedstock, a stream obtained from theneutralized feedstock, the sugar stream, or a combination thereof. 2.The method of claim 1, wherein the lignocellulosic feedstock is selectedfrom the group consisting of corn stover, wheat straw, barley straw,canola straw, rice straw, oat straw, soybean stover, grass, switchgrass, miscanthus, cord grass, and reed canary grass, aspen wood,sawdust, bagasse and beet pulp.
 3. The method of claim 1, wherein thelignocellulosic feedstock contains from about 0.2% to about 4% (w/w)potassium.
 4. The method of claim 1, wherein, in the step of recovering(step d.), the inorganic salt is recovered by ion exclusion.
 5. Themethod of claim 4, wherein the step of recovering (step d.) is followedby crystallization of the inorganic salt, electrodialysis, drying, oragglomeration and granulation.
 6. The method of claim 1, wherein, in thestep of recovering (step d.), the inorganic salt comprises ammoniumsulfate salts, ammonium phosphate salts, potassium sulfate salts,ammonium sulfite salts, potassium sulfite salts, sodium sulfate salts,sodium sulfite salts, magnesium sulfate, ammonium chloride, potassiumchloride, magnesium chloride or a mixture thereof.
 7. The method ofclaim 6, wherein the salt comprises ammonium sulfate salts, potassiumsulfate salts, or a mixture thereof.
 8. The method of claim 6, whereinthe ammonium sulfite salts, sodium sulfite salts, potassium sulfitesalts, or a mixture thereof, are converted to sulfate salts by oxidationbefore or after the step of recovering (step d.).
 9. The method of claim4, wherein the inorganic salt is concentrated by evaporation, membranefiltration, or a combination thereof prior to recovery to produce aconcentrated solution comprising the inorganic salt.
 10. The method ofclaim 9, wherein the concentrated solution is clarified bymicrofiltration, plate and frame filtration, or centrifugation prior torecovery.
 11. The method of claim 1, wherein the step of pretreatment(step a.) comprises a method selected from the group consisting of batchdilute acid hydrolysis, continuous dilute acid hydrolysis, steamexplosion and extrusion.
 12. The method of claim 1, wherein, in the stepof pretreatment (step a.), the one or more than one acid is selectedfrom the group consisting of sulfuric acid, sulfurous acid, sulfurdioxide, phosphoric acid, and a combination thereof.
 13. The method ofclaim 12, wherein the one or more than one acid is sulfuric acid. 14.The method of claim 1, wherein, in the step of adding (step b.), the oneor more than one soluble base is selected from the group consisting ofammonia, ammonium hydroxide, potassium hydroxide, and sodium hydroxide.15. The method of claim 1, wherein the step of pretreating (step a.) isperformed at a temperature from about 160° C. to about 280° C., at a pHfrom about pH 0.4 to about 2.0 and/or for a time period of from about0.1 to about 30 minutes.
 16. The method of claim 1, further comprisingthe steps of: e. fermenting the sugar stream to produce a fermentationbroth comprising ethanol; and f. distilling the fermentation broth toproduce concentrated ethanol and still bottoms.
 17. The method of claim16, further comprising a step of recovering the inorganic salt from thestill bottoms followed by purifying the inorganic salt.
 18. The methodof claim 17, wherein, prior to the step of recovering the inorganic saltfrom the still bottoms, the concentration of the still bottoms isincreased by evaporation, membrane filtration, or a combination thereof,to produce concentrated still bottoms, followed by a step of ionexclusion chromatography using a simulated moving bed (SMB) process. 19.The method of claim 18, wherein the concentrated still bottoms areclarified by microfiltration, plate and frame filtration orcentrifugation, prior to the step of ion exclusion chromatography. 20.The method of claim 19, wherein the step of purifying the inorganic saltcomprises crystallization of the inorganic salt, electrodialysis,drying, or agglomeration and granulation. 21-32. (canceled)